Methyl ester compositions



Patented June 14, 1938 PATENT orrlce METHYL ESTER- COMPOSITIONS Lucas P, Kyrides, Webster Groves, Mm, assignor to Monsanto Chemical Company, St. Louis Mo., a corporation of Delaware No Drawing. Applicationlanuary 9, 1937, Serial No. 119,757

5 Claims.

This invention relates to a novel class of high boiling solvents or plasticizers for cellulose esters, cellulose ethers, natural resins, as well as synthetic resins, the present application being a continuation in part of my co-pending application Serial No. 618,305,fi1ed June 20, 1932, now PatentNo. 2,073,937; attention is drawn to my co-pending application Serial No. 648,986, filed December 27, 1932, now Patent No. 2,073,- 938, and my co-pending application Serial No. 148,737, filed on June 17, 1937,.pertaining to the use of the esters disclosed herein.

In my co-pending applications I have disclosed and claimed a novel class of ester compositions characterized in that they embody esters of oxy acetic acid or its homologues. This invention pertains to esters of the same general class as are disclosed in the applications above identified and which have been found to be particularly well suited to the manufacture of films, lacquers, varnishes, threads, molding compositions, impregnating compositions, etc., for the purpose of imparting desirable characteristics to the ultimate product.

sitions which do polymerize and resinify. These new plasticizers are relatively non-volatile at ordinary temperatures and are compatible with and impart a degree of plasticity, flexibility and resistance to fracture to the ultimate product which may be desired. An outstanding characteristic of the class of compositions contemplated by the present'invention resides in their inordinate degree of compatibility, not only with cellulose derivativesbut also with a large variety of synthetic and natural resins.

In general the novel class of compositions, the use of which-is herein contemplated, consists of neutral esters of carboxylic acids containing one oxy (hydroxy) acetic acid ester group or ester homologues of oxy 'acetic'acid, including glycollic acid, lactic acid, beta oxy propionic acid, alpha and beta oxy butyric acid, etc. These ester compositions may take. group is present, as, for example, in the neutral esters of diglycollic acid or preferably they may takethe form in which the city group is esterifled with an acid group as in the case of'the ethyl glycollate ester of a mono carboxylic aliphatic or aromatic acid such as benzoic acid.

The ester compositions disclosed herein as a form in which an ether case of Another example of compositions which has been found to have inordinate solvent properties is the neutral monoglycollate derivatives of dicarboxylic acids, such, for example, as the ethyl glycollate ester of the mono ethyl ester of phthalic acid which may be represented structurally as follows;

The alcohols which may be employed in preparing the esters may be alkyl or aralkyl alcohols, including cyclic alcohols, as well as an aryl alcohol (phenols) or ether substituted alkyl alcohols such as the mono alkyl ether of glycol, an example of which is the mono ethyl ether of ethylene glycol. In lieu of the phthalic acid one may substitute other dicarboxyiic acids, such acid, it being understood that the invention is not ited to any specific method of preparing the plasticizing compositions.

The mono sodium salt of ethyl phthalate is first prepared by refluxing rapidly, preferably with mechanical agitation, 400 kilos of phthalic anhydride and Sail-liters of absolute ethyl alcohol. The mixture is then allowed to cool to approximately 50 (3., aiter which 159 kilos of anhydrous sodium carbonate are added slowly in order to avoid violent interaction. The resulting mixture is then heated, preferably with agitation, to assure the completion of the reaction. Thereafter 367.5 kilos of ethyl chloracetate (ethyl ester of chior acetic acid) are added slowly while the mixture is agitated and maintained at the I temperature of asteam bath, or preferably at the refluxing temperature.

The resulting reaction mixture is filtered from the sodium chloride which is washed with alco- I101. The alcohol is recovered by distillation and the residual oil is steam distilled for three hours at approximately C. The productso obtained is washed witha sodium carbonate solution until the solution is faintly alkaline to phenolphthalein. If desired the ester may he treated with decolorizing charcoal or activated carbonsuch as "Darco in the usual manner. For this purpose 1% of Darco, based on the weight of the oil product. is uniformly distributed therein after which the mixture is maintained at 90 C. for approximately one hour before removing the carbon by filtration. a

The reaction may be represented as follows:

+o1cH,cooo,H.--

OONa

COOCzHl +Nal The product ethyl phthalyl ethyl glycollate boils at 223-224 C. at 24 mm. without decomposition. It crystallizes at approximately 20 C.

By substituting sodium 'n-butyl phthalate for the sodium ethyl phthalate and n-butyl chlor acetate for the ethyl chlor acetate and otherwise proceeding substantially as described in connection with the ethyl phthalyl ethyl glycollate,

- one obtains butyl phthalyl butyl glycollate havploy an ester of the lower mono chlor substituted ing the formula:

COOC4H,

COOCHiCOOC H which is a colorless liquid that boils at 219 C. at 5 mm. and does not crystallize attemperatures as low as 35 C.

By reacting sodium methyl phthalate with ethyl chlor acetate and otherwise proceeding substantially as described in connection with the ethyl phthalyl ethyl glycollate one obtains the methyl phthalyl ethyl glycollate which is a colorless liquid that boils at 189 C. at 5 mm. and re mains liquid at temperatures as low as 35 C.

and has the possible structural formula:

0000B; oooomcoocm In lieu of the chloracetate ester one may emfatty acids such as chlor propionic acid or a chlor butyric acid.

Obviously, in lieu of the ethyl sodium phthalate employed in the foregoing example, one may prepare the corresponding methyl, propyl, butyl, benzyl, as well as phenyl sodium phthalate. Similarly, in lieu of theethyl ester of chlor acetic acid, one may substitute the chlor acetic acid ester of cresol, phenol or of methyl, pro'pyl, butyl, amyl, or benzyl alcohol, as well as of mono alkyl ether esters of glycol such as the mono ethyl ether ester of ethylene glycol and a dialkyl ether ester of glycerol, etc. The esters of chloracetic acid may be replaced by the esters of other chlor' where R1 is a divalent hydrocarbon radical and R2 is a divalent hydrocarbon radical. When the dicarboxylic acid of the ester is phthalic acid, the group represented in the formula as -COR1-CO would be the phthalyl group;

' in the case of succinic acid the group would be the succinyl group; maleic acid, the maleyl group; chlorphthalic acid, the chlorphthalyl groupyetc. j

' What I claim is:

Y 1. A neutral ester having the formula:

where R1 is a divalent hydrocarbon group, and R2 is a saturated divalent parafflnic, hydrocarbon group.

2. A neutral ester having the formula:

cooom COOCHrCOOCzH:

3. A neutral ester having the formula:

cooion;

ooocznooocnanm 4. A neutral ester having the formula: CHJ-OCOR1-COO-CHzCOO-C:H5

where R1 is a divalent hydrocarbon group. 5. A neutral ester having the formula:

is a. saturated divalent parafllnic hydrocarbon group, and R3 is a saturated monovalent paraffinic hydrocarbon radicaland R4 is a saturated monovalent paraflinic hydrocarbon radical, said ester being further characterized in that R3 and R4 are different monovalent hydrocarbon radi- LUCAS P. KYRIDES. 

